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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2596.
Published online 2009 September 30. doi:  10.1107/S1600536809038951
PMCID: PMC2970422

N-[2-(Amino­carbon­yl)phen­yl]-4-hydr­oxy-2-methyl-2H-1,2-benzothia­zine-3-carboxamide 1,1-dioxide

Abstract

In the title compound, C17H15N3O5S, the thia­zine ring adopts a distorted half-chair conformation. The mol­ecular structure is stabilized by intra­molecular N—H(...)O, N—H(...)N and O—H(...)O hydrogen bonding. Pairs of mol­ecules are bound together as centrosymmetric dimers through N—H(...)O hydrogen bonds.

Related literature

For the synthesis of related mol­ecules, see: Braun (1923 [triangle]); Ahmad et al. (2008 [triangle]); Zia-ur-Rehman et al. (2005 [triangle], 2009 [triangle]). For the biological activity of 1,2-benzothia­zine 1,1-dioxides, see: Bihovsky et al. (2004 [triangle]); Turck et al. (1996 [triangle]); Zia-ur-Rehman et al. (2006 [triangle]). For similar mol­ecules, see: Kojić-Prodić & Rużić-Toroš (1982 [triangle]); Siddiqui et al. (2009 [triangle]); Weast et al. (1984 [triangle]); Zia-ur-Rehman et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2596-scheme1.jpg

Experimental

Crystal data

  • C17H15N3O5S
  • M r = 373.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2596-efi1.jpg
  • a = 8.1377 (6) Å
  • b = 7.0515 (6) Å
  • c = 29.069 (2) Å
  • β = 96.502 (3)°
  • V = 1657.3 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 296 K
  • 0.39 × 0.25 × 0.11 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2007 [triangle]) T min = 0.915, T max = 0.975
  • 16109 measured reflections
  • 3753 independent reflections
  • 3011 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.087
  • wR(F 2) = 0.213
  • S = 1.09
  • 3753 reflections
  • 237 parameters
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038951/bt5073sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038951/bt5073Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are grateful to the PCSIR Laboratories Complex, Lahore, for the provision of facilities necessary to complete this work.

supplementary crystallographic information

Comment

Owing to the verstaile applications of 1,2-benzothiazine 1,1-dioxides, considerable attention has been given to their synthesis since their very first synthesis (Braun, 1923). Among these, Piroxicam (Zia-ur-Rehman et al., 2005), and Meloxicam (Turck et al., 1996) are familiar for their analgesic action and are being used world wide as non-steroidal anti-inflammatory drugs (NSAIDs). Some of the 3,4-dihydro-1,2-benzothiazine-3-carboxylate 1,1-dioxide α-ketomide and P(2)—P(3) peptide mimetic aldehyde compounds act as potent calpain I inhibitors (Bihovsky et al., 2004) while 1,2-benzothiazin-3-yl-quinazolin-4(3H)-ones possess anti-bacterial properties (Zia-ur-Rehman et al., 2006).

In continuation of our work on the synthesis (Zia-ur-Rehman et al., 2006, biological activity (Zia-ur-Rehman et al., 2009) and crystal structures (Zia-ur-Rehman et al., 2007; Ahmad et al., 2008, Siddiqui et al., 2009) of various 1,2-benzothiazine-1,1-dioxides, we herein report the crystal structure of the title compound (I) (Scheme and figure 1). Like its already reported dimethylsulfoxide solvate analogue (Zia-ur-Rehman et al., 2007), thiazine ring involving two double bonds, exhibits sofa conformation; with S1/C1/C2/C7 relatively planar and N1 showing significant departure from plane due to its pyramidal geometry. The enolic hydrogen on O1 is involved in intramolecular hydrogen bonding [O1—H1···O4] with the carbonyl oxygen at C9 giving rise to a six-membered hydrogen bond ring (Table 1). Atom H2 forms hydrogen bonds with both N1 and O5 giving rise to five and six-membered hydrogen bond rings respectively. The C1—S1 [1.755 Å] bond is shorter than a normal C—S single bond (1.81–2.55 Å) (Weast et al., 1984) due to partial double bond character and is in agreement with similar molecules (Kojić-Prodić & Rużić-Toroš, 1982). Each molecule is centrosymmetrically linked to its adjacent one forming a dimer through intermolecular [N—H3B···O5] hydrogen bonds (Fig. 2).

Experimental

N-[2-(Aminocarbonyl)phenyl]-4-hydroxy-2-methyl-2H-1,2-benzothiazine- 3-carboxamide 1,1-dioxide was synthesized according to a literature method (Zia-ur-Rehman et al., 2006). Suitable crystals were obtained by dissoving the compound in chloroform followed by slow evaporation at room temperature.The compound was dissolved in a mixture of methanol and DMSO (80:20 v/v) at room temperature. Crystals were obtained by slow evaporation and dried under high vacuum.

Refinement

All hydrogen atoms were identified in the difference map. They were refined using a riding model with O—H = 0.84 Å, N—H = 0.86 Å, Cmethyl—H 0.98 Å and Caromatic—H = 0.95 Å. and U(H) set to 1.2Ueq of the parent atoms or set to 1.5Ueq(Cmethyl).

Figures

Fig. 1.
The molecular structure of the title compound with displacement ellipsoids at the 50% probability level.
Fig. 2.
Perspective view of the three-dimensional crystal packing showing hydrogen-bonded interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C17H15N3O5SF(000) = 776
Mr = 373.38Dx = 1.496 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6164 reflections
a = 8.1377 (6) Åθ = 2.5–27.1°
b = 7.0515 (6) ŵ = 0.23 mm1
c = 29.069 (2) ÅT = 296 K
β = 96.502 (3)°Needles, colourless
V = 1657.3 (2) Å30.39 × 0.25 × 0.11 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer3753 independent reflections
Radiation source: fine-focus sealed tube3011 reflections with I > 2σ(I)
graphiteRint = 0.039
[var phi] and ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)h = −10→10
Tmin = 0.915, Tmax = 0.975k = −9→9
16109 measured reflectionsl = −32→37

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.087Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.213H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0335P)2 + 9.427P] where P = (Fo2 + 2Fc2)/3
3753 reflections(Δ/σ)max < 0.001
237 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = −0.40 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.35684 (14)0.5031 (2)0.33289 (4)0.0343 (3)
O20.2977 (5)0.6850 (5)0.34450 (12)0.0427 (9)
O30.5306 (4)0.4668 (7)0.33922 (13)0.0538 (11)
O4−0.1641 (4)0.3152 (6)0.38428 (12)0.0480 (10)
O50.3670 (4)0.3198 (6)0.47838 (12)0.0484 (10)
N10.2640 (5)0.3427 (6)0.36214 (13)0.0310 (9)
N20.0743 (5)0.2848 (6)0.43247 (12)0.0306 (8)
H20.18010.28260.43280.037*
N30.3804 (6)0.4241 (8)0.55160 (15)0.0534 (13)
H3A0.48170.45850.55130.064*
H3B0.33190.44070.57610.064*
O1−0.1513 (4)0.3895 (6)0.29823 (12)0.0436 (9)
H1−0.19680.37470.32180.065*
C10.2765 (6)0.4493 (7)0.27578 (16)0.0329 (10)
C20.1069 (6)0.4046 (7)0.26901 (16)0.0322 (10)
C30.0347 (8)0.3766 (8)0.22406 (17)0.0445 (13)
H3−0.07800.35160.21830.053*
C40.1301 (9)0.3861 (9)0.18781 (19)0.0577 (17)
H40.08050.36850.15770.069*
C50.2966 (9)0.4210 (10)0.19540 (19)0.0580 (17)
H50.35940.42210.17060.070*
C60.3718 (7)0.4546 (9)0.23979 (19)0.0470 (14)
H60.48450.48020.24510.056*
C70.0124 (6)0.3801 (7)0.30885 (16)0.0314 (10)
C80.0874 (6)0.3479 (7)0.35254 (16)0.0308 (10)
C9−0.0106 (6)0.3133 (7)0.39093 (15)0.0315 (10)
C100.0150 (6)0.2579 (6)0.47583 (15)0.0287 (9)
C110.1236 (6)0.2888 (7)0.51660 (16)0.0323 (10)
C120.0636 (7)0.2643 (7)0.55876 (17)0.0402 (12)
H120.13500.28100.58580.048*
C13−0.0980 (7)0.2160 (8)0.56205 (18)0.0441 (13)
H13−0.13580.20460.59090.053*
C14−0.2039 (7)0.1845 (8)0.5223 (2)0.0448 (13)
H14−0.31340.15140.52450.054*
C15−0.1485 (6)0.2019 (7)0.47945 (17)0.0374 (11)
H15−0.21970.17640.45280.045*
C160.2986 (6)0.3449 (8)0.51412 (16)0.0368 (11)
C170.3393 (7)0.1508 (9)0.3632 (2)0.0521 (15)
H17A0.30250.07900.38820.078*
H17B0.45760.16190.36780.078*
H17C0.30650.08730.33440.078*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0273 (5)0.0450 (7)0.0309 (6)−0.0003 (5)0.0047 (4)0.0006 (5)
O20.048 (2)0.041 (2)0.0391 (19)−0.0070 (17)0.0065 (16)−0.0037 (16)
O30.0284 (18)0.084 (3)0.049 (2)0.000 (2)0.0067 (16)0.010 (2)
O40.0289 (18)0.079 (3)0.0368 (19)0.0027 (19)0.0076 (14)0.0050 (19)
O50.0350 (19)0.075 (3)0.0354 (19)−0.0012 (19)0.0067 (15)−0.0072 (19)
N10.0278 (19)0.038 (2)0.0276 (19)0.0065 (17)0.0039 (15)0.0006 (16)
N20.0260 (19)0.039 (2)0.0280 (19)0.0001 (17)0.0063 (15)0.0053 (17)
N30.042 (3)0.082 (4)0.036 (2)−0.006 (3)0.0011 (19)−0.009 (2)
O10.0307 (18)0.065 (3)0.0335 (18)−0.0013 (18)−0.0011 (14)0.0024 (18)
C10.040 (3)0.032 (2)0.028 (2)0.001 (2)0.0079 (19)0.0016 (18)
C20.037 (2)0.031 (2)0.029 (2)−0.001 (2)0.0064 (19)0.0005 (19)
C30.063 (4)0.042 (3)0.029 (2)−0.005 (3)0.005 (2)−0.002 (2)
C40.087 (5)0.056 (4)0.029 (3)−0.013 (3)0.004 (3)−0.005 (3)
C50.076 (4)0.071 (4)0.031 (3)−0.005 (4)0.024 (3)−0.004 (3)
C60.046 (3)0.057 (4)0.041 (3)−0.003 (3)0.016 (2)−0.001 (3)
C70.030 (2)0.034 (2)0.030 (2)0.0008 (19)0.0067 (18)−0.0015 (19)
C80.028 (2)0.034 (2)0.030 (2)0.0032 (19)0.0029 (17)0.0000 (19)
C90.034 (2)0.032 (2)0.029 (2)0.0000 (19)0.0034 (18)−0.0003 (19)
C100.032 (2)0.026 (2)0.028 (2)0.0039 (18)0.0082 (18)0.0025 (18)
C110.039 (3)0.028 (2)0.031 (2)0.004 (2)0.0072 (19)0.0029 (19)
C120.058 (3)0.035 (3)0.029 (2)0.002 (2)0.011 (2)0.001 (2)
C130.063 (4)0.039 (3)0.035 (3)0.000 (3)0.023 (2)0.003 (2)
C140.045 (3)0.039 (3)0.054 (3)−0.002 (2)0.021 (3)0.005 (3)
C150.036 (3)0.039 (3)0.039 (3)0.000 (2)0.012 (2)0.007 (2)
C160.034 (3)0.044 (3)0.031 (2)0.006 (2)−0.0011 (19)0.003 (2)
C170.052 (3)0.049 (3)0.058 (4)0.020 (3)0.020 (3)0.014 (3)

Geometric parameters (Å, °)

S1—O21.424 (4)C4—C51.371 (9)
S1—O31.428 (4)C4—H40.9300
S1—N11.648 (4)C5—C61.384 (8)
S1—C11.755 (5)C5—H50.9300
O4—C91.242 (6)C6—H60.9300
O5—C161.246 (6)C7—C81.364 (6)
N1—C81.433 (6)C8—C91.464 (6)
N1—C171.484 (7)C10—C151.403 (6)
N2—C91.337 (6)C10—C111.413 (6)
N2—C101.412 (5)C11—C121.380 (6)
N2—H20.8600C11—C161.488 (7)
N3—C161.333 (6)C12—C131.372 (8)
N3—H3A0.8600C12—H120.9300
N3—H3B0.8600C13—C141.378 (8)
O1—C71.335 (5)C13—H130.9300
O1—H10.8200C14—C151.379 (7)
C1—C61.372 (7)C14—H140.9300
C1—C21.407 (7)C15—H150.9300
C2—C31.385 (7)C17—H17A0.9600
C2—C71.471 (6)C17—H17B0.9600
C3—C41.379 (8)C17—H17C0.9600
C3—H30.9300
O2—S1—O3119.2 (3)O1—C7—C2114.2 (4)
O2—S1—N1108.0 (2)C8—C7—C2122.3 (4)
O3—S1—N1108.4 (2)C7—C8—N1121.2 (4)
O2—S1—C1108.6 (2)C7—C8—C9120.8 (4)
O3—S1—C1109.9 (2)N1—C8—C9117.9 (4)
N1—S1—C1101.3 (2)O4—C9—N2123.4 (4)
C8—N1—C17115.4 (4)O4—C9—C8120.3 (4)
C8—N1—S1113.0 (3)N2—C9—C8116.3 (4)
C17—N1—S1115.1 (3)C15—C10—N2121.8 (4)
C9—N2—C10129.2 (4)C15—C10—C11119.3 (4)
C9—N2—H2115.4N2—C10—C11118.9 (4)
C10—N2—H2115.4C12—C11—C10118.4 (5)
C16—N3—H3A120.0C12—C11—C16120.9 (5)
C16—N3—H3B120.0C10—C11—C16120.8 (4)
H3A—N3—H3B120.0C13—C12—C11122.1 (5)
C7—O1—H1109.5C13—C12—H12119.0
C6—C1—C2122.0 (5)C11—C12—H12119.0
C6—C1—S1122.2 (4)C12—C13—C14119.7 (5)
C2—C1—S1115.8 (3)C12—C13—H13120.2
C3—C2—C1118.0 (5)C14—C13—H13120.2
C3—C2—C7121.5 (5)C13—C14—C15120.4 (5)
C1—C2—C7120.5 (4)C13—C14—H14119.8
C4—C3—C2119.9 (6)C15—C14—H14119.8
C4—C3—H3120.1C14—C15—C10120.2 (5)
C2—C3—H3120.1C14—C15—H15119.9
C5—C4—C3121.2 (5)C10—C15—H15119.9
C5—C4—H4119.4O5—C16—N3120.8 (5)
C3—C4—H4119.4O5—C16—C11121.6 (4)
C4—C5—C6120.4 (5)N3—C16—C11117.6 (4)
C4—C5—H5119.8N1—C17—H17A109.5
C6—C5—H5119.8N1—C17—H17B109.5
C1—C6—C5118.5 (5)H17A—C17—H17B109.5
C1—C6—H6120.7N1—C17—H17C109.5
C5—C6—H6120.7H17A—C17—H17C109.5
O1—C7—C8123.6 (4)H17B—C17—H17C109.5
O2—S1—N1—C858.6 (4)O1—C7—C8—C92.6 (8)
O3—S1—N1—C8−171.0 (3)C2—C7—C8—C9−176.4 (4)
C1—S1—N1—C8−55.4 (4)C17—N1—C8—C7−96.6 (6)
O2—S1—N1—C17−165.8 (4)S1—N1—C8—C738.8 (6)
O3—S1—N1—C17−35.4 (4)C17—N1—C8—C982.0 (5)
C1—S1—N1—C1780.2 (4)S1—N1—C8—C9−142.6 (4)
O2—S1—C1—C6106.1 (5)C10—N2—C9—O4−2.0 (8)
O3—S1—C1—C6−25.9 (5)C10—N2—C9—C8176.5 (4)
N1—S1—C1—C6−140.4 (5)C7—C8—C9—O4−0.9 (8)
O2—S1—C1—C2−72.5 (4)N1—C8—C9—O4−179.6 (5)
O3—S1—C1—C2155.5 (4)C7—C8—C9—N2−179.5 (5)
N1—S1—C1—C241.0 (4)N1—C8—C9—N21.9 (7)
C6—C1—C2—C3−3.9 (8)C9—N2—C10—C1519.3 (8)
S1—C1—C2—C3174.7 (4)C9—N2—C10—C11−160.5 (5)
C6—C1—C2—C7173.4 (5)C15—C10—C11—C12−0.6 (7)
S1—C1—C2—C7−8.0 (6)N2—C10—C11—C12179.2 (4)
C1—C2—C3—C42.4 (8)C15—C10—C11—C16178.9 (4)
C7—C2—C3—C4−174.9 (5)N2—C10—C11—C16−1.3 (7)
C2—C3—C4—C50.7 (10)C10—C11—C12—C13−1.7 (8)
C3—C4—C5—C6−2.4 (11)C16—C11—C12—C13178.8 (5)
C2—C1—C6—C52.2 (9)C11—C12—C13—C142.2 (8)
S1—C1—C6—C5−176.3 (5)C12—C13—C14—C15−0.2 (8)
C4—C5—C6—C10.9 (10)C13—C14—C15—C10−2.1 (8)
C3—C2—C7—O1−20.1 (7)N2—C10—C15—C14−177.3 (5)
C1—C2—C7—O1162.7 (5)C11—C10—C15—C142.5 (7)
C3—C2—C7—C8159.0 (5)C12—C11—C16—O5160.7 (5)
C1—C2—C7—C8−18.2 (7)C10—C11—C16—O5−18.7 (8)
O1—C7—C8—N1−178.8 (4)C12—C11—C16—N3−19.5 (7)
C2—C7—C8—N12.1 (7)C10—C11—C16—N3161.1 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O40.821.852.569 (5)145
N2—H2···O50.861.922.607 (5)136
N2—H2···N10.862.282.728 (5)113
N3—H3A···O5i0.862.222.941 (6)141

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5073).

References

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